Polymeric poly-phosphorus additives for: gear oil, grease, engine-oil, combustion-engine lubricant, automatic transmission fluid, anti-wear agents, two-cycle engine lubricant, or marine-engine lubricant

ABSTRACT

A method having the step of using a compound as an additive for: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent, the compound having the structure: 
                         
wherein each R is an independently selected alkylphenol-free moiety that is a C 1-22  alkyl, C 6-40  cycloalkyl, C 3-20  methoxy alkyl glycol ether, C 3-20  alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C 2-40  alkylene, C 6-40  cycloalkylene, C 2-20  alkylene glycol ether, or C 3-40  alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority to U.S. provisional patent application 62/779,219 having a filing date of Dec. 13, 2018. The subject matter of U.S. provisional patent application 62/779,219 is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

The following are all known: gear oils, greases, engine-oil additives, combustion-engine lubricants, automatic transmission fluids, anti-wear agents, two-cycle engine lubricants, and marine-engine lubricants. With all of them, there is a need for improved performance.

BRIEF SUMMARY OF THE INVENTION

A method having the step of using a compound as an additive for: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.

A method having the step of using a compound as an additive for: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 2 to 100; and wherein x is an integer ranging from 1 to 1000.

A method having the step of using a compound as an additive for: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 2 to 100; and wherein x is an integer ranging from 1 to 1000.

A method having the step of using a compound as an additive for: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 2 to 100; wherein each Z is independently selected from the group consisting of S and O; and wherein x is an integer ranging from 1 to 1000.

A method having the step of using a copolymer compound as an additive for: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein Y₁ and Y₂ are different; wherein each m is an independently selected integer ranging from 1 to 100; wherein each Z is independently selected from the group consisting of S, H, O, and nothing; and wherein each x is an independently selected integer ranging from 1 to 1000.

A method having the step of using a compound as an additive for: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIG. 1 is a picture of a Timken testing apparatus.

FIG. 2 is a graph showing Falex Pin and Vee Block test results.

FIG. 3 is a graph showing Falex Pin and Vee Block test results.

FIG. 4 is a graph showing Falex Pin and Vee Block test results.

FIG. 5 is a graph showing Falex Pin and Vee Block test results.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments are directed to compounds that are useful as additives for: gear oil, grease, engine-oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, and marine-engine lubricant. The compounds are also useful as an anti-wear additive or anti-wear agent.

An embodiment is directed to polyhydrogen-phosphite compounds having the general structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety;

wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety;

wherein each m is an independently selected integer ranging from 1 to 100; and

wherein x is an integer ranging from 1 to 1000.

In some polyhydrogen-phosphite embodiments, each Y is an independently selected ethylene, propylene, cyclohexene dimethanol, or caprylene lactone moiety.

In some polyhydrogen-phosphite embodiments, the compound has a weight ranging from 1000 to 30000 Daltons. In some polyhydrogen-phosphite embodiments, the compound has a weight ranging from 400 to 30000 Daltons. In some polyhydrogen-phosphite embodiments, the compound has a weight ranging from 500 to 30000 Daltons.

An embodiment is directed to phosphate compounds having the general structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety;

wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety;

wherein each m is an independently selected integer ranging from 1 to 100; and

wherein x is an integer ranging from 1 to 1000.

In some phosphate embodiments, each Y is an independently selected ethylene, propylene, cyclohexene dimethanol, or caprylene lactone moiety.

In some phosphate embodiments, the compound has a weight ranging from 1000 to 30000 Daltons. In some phosphate embodiments, the compound has a weight ranging from 400 to 30000 Daltons. In some phosphate embodiments, the compound has a weight ranging from 500 to 30000 Daltons.

An embodiment is directed to thiophosphate compounds having the general structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety;

wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆-40 cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety;

wherein each m is an independently selected integer ranging from 1 to 100; and

wherein x is an integer ranging from 1 to 1000.

In some thiophosphate embodiments, each Y is an independently selected ethylene, propylene, cyclohexene dimethanol, or caprylene lactone moiety.

In some thiophosphate embodiments, the compound has a weight ranging from 1000 to 30000 Daltons. In some thiophosphate embodiments, the compound has a weight ranging from 400 to 30000 Daltons. In some thiophosphate embodiments, the compound has a weight ranging from 500 to 30000 Daltons.

An embodiment is directed to phosphorus-containing compounds having the general structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety;

wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆-40 cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety;

wherein each m is an independently selected integer ranging from 1 to 100;

wherein each Z is independently selected from the group consisting of S and O; and

wherein x is an integer ranging from 1 to 1000.

In some phosphorus-containing embodiments, each Y is an independently selected ethylene, propylene, cyclohexene dimethanol, or caprylene lactone moiety.

In some phosphorus-containing-compound embodiments, the compound has a weight ranging from 1000 to 30000 Daltons. In some phosphorus-containing embodiments, the compound has a weight ranging from 400 to 30000 Daltons. In some phosphorus-containing embodiments, the compound has a weight ranging from 500 to 30000 Daltons.

An embodiment is directed to phosphorus-containing copolymer compounds having the general structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety;

wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety;

wherein Y₁ and Y₂ are different;

wherein each m is an independently selected integer ranging from 1 to 100;

wherein each Z is independently selected from the group consisting of S, H, O, and nothing; and

wherein each x is an independently selected integer ranging from 1 to 1000.

In some phosphorus-containing copolymer embodiments, each Y is an independently selected ethylene, propylene, cyclohexene dimethanol, or caprylene lactone moiety.

In some embodiments, each Z is independently selected from the group consisting of S, H, and 0.

In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from 1000 to 30000 Daltons. In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from 400 to 30000 Daltons. In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from 500 to 30000 Daltons.

An embodiment is directed to phosphite compounds having the general structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety;

wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆-40 cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety;

wherein each m is an independently selected integer ranging from 1 to 100; and

wherein x is an integer ranging from 1 to 1000.

In some phosphite embodiments, each Y is an independently selected ethylene, propylene, cyclohexene dimethanol, or caprylene lactone moiety.

In some phosphorus-compound embodiments, the compound has a weight ranging from 1000 to 30000 Daltons. In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from 400 to 30000 Daltons. In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from 500 to 30000 Daltons.

Methods for manufacturing any of the disclosed compounds that include phosphite compounds, polyhydrogen phosphite compounds, phosphate compounds, thiophosphate compounds, and thiophosphite-phosphate copolymer compounds can be determined by persons of ordinary skill in the art without having to exercise undue experimentation. Non-limiting examples of manufacturing methods can be found in the below Examples.

Any of the above compounds, either alone or in any combination, can be used as an additive for: gear oil, grease, engine-oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, or marine-engine lubricant. The compounds, either alone or in any combination, are also useful as anti-wear additives. For each of the described uses, useful amounts of the compound(s) can be determined by persons of ordinary skill in the art. As a non-limiting example, useful amounts of the above compounds, either alone or in any combination, range from 5 to 10% by weight of the fluid to which the compound(s) is being added. In an additional non-limiting example, useful amounts of the above compound(s), either alone or in any combination, range from 0.5 to 20% by weight of the fluid to which the compound(s) is being added.

In any of the above sulfur-containing compounds, the amount of sulfur within the compound can range from 50 to 100 mole percent relative to the amount of phosphorus within the compound; stated differently, in any of the above sulfur-containing compounds, anywhere from half to all of the phorphorus atoms are bonded to a sulfur atom. In another embodiment, the amount of sulfur within the compound can range from 90 to 100 mole percent relative to the amount of phosphorus within the compound. In another embodiment, the amount of sulfur within the compound is 100 mole percent relative to the amount of phosphorus within the compound.

Although all of the above compounds are taught as having alkylphenol-free moieties, in some embodiments, a compound's above-described alkylphenol-free moiety is replaced with an alkylphenol moiety. In other embodiments, more than one of a compound's above-described alkylphenol-free moieties is replaced with an alkylphenol moieties. Here is a non-limiting example of a compound containing an alkylphenol moiety:

wherein each R is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.

Here is another non-limiting example of a compound containing an alkylphenol moiety:

wherein each R is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.

Here is another non-limiting example of a compound containing an alkylphenol moiety:

wherein each R is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.

Here is another non-limiting example of a compound containing an alkylphenol moiety:

wherein each R is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; wherein each Z is independently selected from the group consisting of S and O; and wherein x is an integer ranging from 1 to 1000.

Here is another non-limiting example of a compound containing an alkylphenol moiety:

wherein each R is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; wherein each Z is independently selected from the group consisting of S and O; and wherein each x is an independently selected integer ranging from 1 to 1000.

Here is another non-limiting example of a compound containing an alkylphenol moiety:

wherein each R is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₃₋₂₀ methoxy alkyl glycol ether, C₃₋₂₀ alkyl glycol ether, or Y—OH moiety; wherein each Y is an independently selected alkylphenol moiety or an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene, C₆₋₄₀ cycloalkylene, C₂₋₂₀ alkylene glycol ether, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.

In an embodiment, using a compound as an additive for gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent means adding the compound to a gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent. In another embodiment, using a compound as an additive for gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent means using the end composition that includes the compound as a gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent.

Examples I

TNPP-T (Trisnonylphenyl thiophosphate)

To a three-neck 250 mL flask equipped with a mechanical stirrer and purged with nitrogen was added 75.83 grams of triisnonylphenol phosphite (0.110 mol), with a total nonylphenol content ranging from 0.05% to 0.5% with 0.1% being the target and 0.39 grams of 2,5-dimercapto-1,3,4-thiadiazole (0.0026 mol). The mixture was mixed well and heat was applied to a reaction temperature of 240° F. 3.37 grams of elemental sulfur (0.130 mol) was then added at this temperature. After one hour, the reaction temperature is increased to 280° F. and held for 16-24 hours. This reaction takes place under a nitrogen blanket. The resulting thiophosphate had the following analysis:

% Phosphorous 4.5 % Sulfur 4.2 Density 20 C 1.01 Color, APHA 50 % Nonylphenol <0.20

LGP-11-T (Alkylphenol Free Polymeric Polyphosphite), U.S. Pat. No. 8,563,637B

To a three-neck 250 mL flask equipped with a mechanical stirrer and purged with nitrogen was added 75.83 grams of a alkylphenol-free liquid polymeric phosphite (Example #2 from U.S. Pat. No. 8,563,637), with a molecular weight of about 9100 and 0.39 grams of 2,5-dimercapto-1,3,4-thiadiazole (0.0026 mol). The mixture was mixed well and heat was applied to a reaction temperature of 240° F. Then 3.51 grams of elemental sulfur (0.109 mol) was added. After one hour, the reaction temperature is increased to 280° F. and held for 16-24 hours. This reaction takes place under a nitrogen blanket. The resulting alkyl phenol free polymeric thiophosphate had the following analysis:

% Phosphorous 4.7 % Sulfur 4.4 Density 20 C Color, APHA 60 % Nonylphenol 0

LGP-12-T (Alkylphenol Free Cycloaliphatic Poly and Copoly Phosphites) U.S. Pat. No. 8,981,042B2

To a three-neck 250 mL flask equipped with a mechanical stirrer and purged with nitrogen was added 75.83 grams of cycloaliphatic polyphosphite (Example 2 from U.S. Pat. No. 8,981,042) with a molecular weight range of about 14,000 and 0.39 grams of 2,5-dimercapto-1,3,4-thiadiazole (0.0026 mol). The mixture was mixed well and heat was applied to a reaction temperature of 240° F. 5.52 grams of elemental sulfur (0.172 mol) was then added. After one hour, the reaction temperature is increased to 280° F. and held for 16-24 hours. This reaction takes place under a nitrogen blanket. The resulting analysis of the phenol free cycloaliphatic alkylated poly thiophosphate was:

% Phosphorous 7.2 % Sulfur 6.75 Color, APHA 50 % Nonylphenol 0

LGP(DPG)-11-T, U.S. Pat. No. 8,563,637B

To a three-neck 250 mL flask equipped with a mechanical stirrer and purged with nitrogen was added 75.83 grams of a alkylphenol-free liquid polymeric phosphite (Example #3 from U.S. Pat. No. 8,563,637), with a molecular weight of about 1200 and 0.39 grams of 2,5-dimercapto-1,3,4-thiadiazole (0.0026 mol). The mixture was mixed well and heat was applied to a reaction temperature of 240° F. Then 6.29 grams of elemental sulfur (0.196 mol) was added. After one hour, the reaction temperature is increased to 280° F. and held for 16-24 hours. This reaction takes place under a nitrogen blanket. The resulting alkyl phenol free polymeric thiophosphate had the following analysis:

% Phosphorous 7.8 % Sulfur 7.6 Color, APHA 60 % Nonylphenol 0

DP-6T (Triisodecyl Phosphite) Doverphos 6

To a three-neck 250 mL flask equipped with a mechanical stirrer and purged with nitrogen was added 75.83 grams of a Triisodecyl phosphite, with a molecular weight of about 500 and 0.39 grams of 2,5-dimercapto-1,3,4-thiadiazole (0.0026 mol). The mixture was mixed well and heat was applied to a reaction temperature of 240° F. Then 4.87 of elemental sulfur (0.152 mol) was added. After one hour, the reaction temperature is increased to 280° F. and held for 16-24 hours. This reaction takes place under a nitrogen blanket. The resulting alkyl phenol free thiophosphate had the following analysis:

% Phosphorous 6.2 % Sulfur 6.0 Color, APHA 60 % Nonylphenol 0

Testing Methodology

Four Ball Wear: This test is used for evaluating friction-reducing and anti-wear fluids. Testing involves 3 stationary steel balls secured in a steel cup and a 4^(th) steel ball lowered to make contact with the 3 stationary balls. The fluid to be tested is poured into the cup. The 4^(th) ball is the only ball that spins. Typical rpm for the ball is 1200 rpm. The single ball spins in contact with the 3 stationary balls at a constant load of 40 kg. Typical run time is 1 hour. The wear on the lower 3 balls is measured and reported in mm. The fluid to produce the smallest wear scars has the best performance.

Parameter Setting Load (kg) 40 Temperature Ambient Time (min) 60 Dilution Rate 5% Speed (rpm) 1,200  

Wear Scar (mm)

Ball Example 1 Example 2 Example 3 Example 4 Example 5 1 0.91 0.39 0.52 0.52 0.57 2 0.91 0.39 0.52 0.52 0.55 3 0.86 0.39 0.52 0.52 0.55 Avg. mm 0.89 0.39 0.52 0.52 0.55

Test results clearly show that the alkylphenol free polymeric polyphosphites give excellent results, better than the commercial trisnonylphenyl thiophosphate with excellent color. And there are no alkylphenols in the final products.

Timken Testing: Timken testing was carried out by adding weight to a lever applying pressure to a block that is in contact with a wheel. The bottom portion of the wheel is submersed in the fluid to be tested. As the wheel spins, the lubricant is carried to the interface of the block and wheel. A one pound weight is added to the lever every minute until a maximum of 13 pounds has been added. The wear scar on the block is measured and reported in millimeters. See FIG. 1.

Wear Scar (mm)

Example 1 Example 2 Example 3 Example 4 Example 5 2.34 2.08 2.08 2.24 2.60

Test results clearly show that the alkylphenol free polymeric polyphosphites give excellent results, better than the commercial trisnonylphenyl thiophosphate with excellent color. And there are no alkylphenols in the final products.

Examples II

The following formulae were prepared for various machine testing:

Oil Based Formulae

Conc. % Methyl Additive Functionality By Weight Ester Added Paroil 152 Chlorinated Paraffin 5 7 Mayfree 133 Phosphate Amide 2.6 4.4 Doverphos 253 Di-oleyl Hydrogen 2.6 7 Phosphite Doverphos 53 Tri-lauryl Phosphite 2.6 7 Doverphos 50 Phosphite 2.6 7 Complex Ester 5% Ester 5 0 Complex Ester 10% Ester 10 0 Complex Ester 25% Ester 25 0 Alkylphenol Free Phosphite 2.6 7 Polymeric Phosphite A Alkylphenol Free Phosphite 2.6 7 Polymeric Phosphite B Base 10SE Sulfurized Ester 5 2 Alkylphenol Free Phos & Sulfur 5 7 Polymeric Thiophosphate A Alkylphenol Free Phos & Sulfur 5 7 Polymeric Thiophosphate B ZDDP Phos, Sulfur & Zinc 2.6 7

Water Based Formulae

The water based formulae were prepared using a commercial semi-synthetic. The additive was added to either the Super Concentrate (SC) prior to dilution of the semi-synthetic with water, or to the concentrate after 50% dilution of the semi-synthetic with water. After the 50% dilution with water, all testing was conducted with the semi-synthetic diluted in water at 5%.

% Added % Added to Final Additive to S.C. Concentrate Conc. % Paroil 152 5 0 5 Mayfree 133 0 2.6 5 Doverphos 253 0 2.6 5 Doverphos 53 0 2.6 5 Dovephos 50 0 2.6 5 Complex Ester 5% 0 5 5 Alkylphenol Free 0 2.6 5 Polymeric Phosphite A Alkylphenol Free 0 2.6 5 Polymeric Phosphite B

Testing Methodology

Oil Based Testing:

Four Ball Wear: This test is used for evaluating friction-reducing and anti-wear fluids. Testing involves 3 stationary steel balls secured in a steel cup and a 4^(th) steel ball lowered to make contact with the 3 stationary balls. The fluid to be tested is poured into the cup. The 4^(th) ball is the only ball that spins. Typical rpm for the ball is 1200 rpm. The single ball spins in contact with the 3 stationary balls at a constant load of 40 kg. Typical run time is 1 hour. The wear on the lower 3 balls is measured and reported in mm. The fluid to produce the smallest wear scars has the best performance.

Parameter Setting Load (kg) 40 Temperature Ambient Time (min) 60 Speed (rpm) 1,200  

Wear Scar (mm)

Additive Average Wear, mm Paroil 152, Std. 0.99 Doverphos 53 0.41 ZDDP 0.45 Base 10SE 0.52 Doverphos 253 0.54 Mayfree 133 0.61 Alkylphenol Free Polymeric 0.36 Phosphite A Alkylphenol Free Polymeric 0.49 Phosphite B Doverphos 50 0.46 Alkylphenol Free Polymeric 0.36 Thiophosphate A Alkylphenol Free Polymeric 0.39 Thiophosphate B Polymeric Ester-5% 0.66 Polymeric Ester-10% 0.65 Polymeric Ester-25% 0.53

Vertical Drawbead: Vertical Drawbead is a machine used to determine a fluids ability to form a piece of metal. Vertical Drawbead works by applying pressure to a coated metal strip. The formulae to be tested is applied to a 24 inch metal strip which is raised between two dye. The dyes apply 500 psi of pressure to the bottom of the strip. The coated strip is pulled between the two dyes. The amount of force needed to pull the strip between the dyes, is plotted by an X-Y plotter and the force is calculated from this curve. In all cases, higher percent efficiency refers to the performance of the fluid being better.

In this test, all formulae were evaluated on 1018 Steel and 316 Stainless Steel.

316 Stainless Steel

Additive % Efficiency Paroil 152, Std. 100.0 Doverphos 53 95.1 ZDDP 103.8 Base 10SE 81.0 Doverphos 253 77.3 Mayfree 133 102.2 Alkylphenol Free Polymeric 70.3 Phosphite A Alkylphenol Free Polymeric 46.4 Phosphite B Doverphos 50 103.8 Alkylphenol Free Polymeric 114.2 Thiophosphate A Alkylphenol Free Polymeric 119.0 Thiophosphate B Polymeric Ester-5% 112.5 Polymeric Ester-10% 116.8 Polymeric Ester-25% 147.6

1018 Steel

Additive % Efficiency Paroil 152, Std. 100.0 Doverphos 53 109.4 ZDDP 103.8 Base 10SE 103.3 Doverphos 253 105.4 Mayfree 133 97.1 Alkylphenol Free Polymeric 103.5 Phosphite A Alkylphenol Free Polymeric 102.3 Phosphite B Doverphos 50 111.6 Alkylphenol Free Polymeric 107.0 Thiophosphate A Alkylphenol Free Polymeric 102.3 Thiophosphate B Polymeric Ester-5% 111.9 Polymeric Ester-10% 113.1 Polymeric Ester-25% 129.5

Microtap Tap and Torque Testing: Microtap testing is one method used to determine a fluids ability to remove metal. A metal bar with predrilled holes is fastened to a vice. The tap and the metal bar are coated in the fluid to be tested. The tap rotates to tap out the pre-drilled hole. The force needed to tap the hole is measured by a computer and is reported as torque in newton centimeters. In all cases, higher percent efficiency refers to the performance of the fluid being better.

In this test, all formulae were evaluated on 1018 Steel.

1018 Steel

Additive % Efficiency Paroil 152, Std. 100.0 Doverphos 53 101.7 ZDDP 101.1 Base 10SE 100.5 Doverphos 253 101.1 Mayfree 133 103.8 Alkylphenol Free Polymeric 103.1 Phosphite A Alkylphenol Free Polymeric 102.9 Phosphite B Doverphos 50 103.8 Alkylphenol Free Polymeric 103.5 Thiophosphate A Alkylphenol Free Polymeric 104.3 Thiophosphate B Polymeric Ester-5% 105.2 Polymeric Ester-10% 104.0 Polymeric Ester-25% 106.9

Falex Pin and Vee Block Testing: Falex Pin and Vee Block measures the fluids ability to perform in more severe operations, such as cold heading, but can also apply to grinding operations. A pin is fastened using a brass shear pin. Two Vee blocks are clamped onto the pin. The pin and vee blocks are submerged in the fluid to be tested. The load applied on the pin from the vee blocks begins at 250 pounds. The load is increased automatically by a ratcheting arm as the pin spins between the two vee blocks. The torque generated by the load on the pin is read at 250 pound load and is recorded every 250 pounds until a final load of 4500 pounds is reached or a failure occurs. A failure implies the pin or shear pin has broken. See FIGS. 2 and 3.

Water Based Testing:

Microtap Tap and Torque Testing: Microtap testing is one method used to determine a fluids ability to remove metal. A metal bar with predrilled holes is fastened to a vice. The tap and the metal bar are coated in the fluid to be tested. The tap rotates to tap out the predrilled hole. The force needed to tap the hole is measured by a computer and is reported as torque in newton centimeters. In all cases, higher percent efficiency refers to the performance of the fluid being better.

In this test, all formulae were evaluated on 1018 Steel and 316 Stainless Steel.

316 Stainless Steel

Additive % Efficiency Paroil 152, Std. 100.0 Doverphos 53 108.6 Doverphos 253 112.0 Mayfree 133 117.6 Alkylphenol Free Polymeric 109.4 Phosphite A Alkylphenol Free Polymeric 112.1 Phosphite B Doverphos 50 109.4 Polymeric Ester-5% 107.6

1018 Steel

Additive % Efficiency Paroil 152, Std. 100.0 Doverphos 53 102.4 Doverphos 253 101.1 Mayfree 133 101.9 Alkylphenol Free Polymeric 100.9 Phosphite A Alkylphenol Free Polymeric 100.2 Phosphite B Doverphos 50 100.0 Polymeric Ester-5% 99.3

Falex Pin and Vee Block Testing: Falex Pin and Vee Block measures the fluids ability to perform in more severe operations, such as cold heading, but can also apply to grinding operations. A pin is fastened using a brass shear pin. Two Vee blocks are clamped onto the pin. The pin and vee blocks are submerged in the fluid to be tested. The load applied on the pin from the vee blocks begins at 250 pounds. The load is increased automatically by a ratcheting arm as the pin spins between the two vee blocks. The torque generated by the load on the pin is read at 250 pound load and is recorded every 250 pounds until a final load of 4500 pounds is reached or a failure occurs. A failure implies the pin or shear pin has broken. See FIGS. 4 and 5. 

What is claimed is:
 1. A method comprising the step: adding a compound in an amount ranging from 0.5% to 10% by weight to: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent; to thereby improve the respective anti-wear properties, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₆ alkyl moiety, C₆ cycloalkyl moiety, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene moiety, C₆₋₄₀ cycloalkylene moiety, C₂₋₂₀ alkylene glycol ether moiety, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to
 1000. 2. The method of claim 1, wherein each Y is an independently selected ethylene moiety, propylene moiety, cyclohexene dimethanol moiety, or caprylene lactone moiety.
 3. The method of claim 1, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
 4. The method of claim 1, wherein the compound has a weight ranging from 400 to 30000 Daltons.
 5. The method of claim 1, wherein the compound has a weight ranging from 500 to 30000 Daltons.
 6. A method comprising the step: adding a compound to: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent; to thereby improve the respective anti-wear properties, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl moiety, C₆₋₄₀ cycloalkyl moiety, C₃₋₂₀ methoxy alkyl glycol ether moiety, C₃₋₂₀ alkyl glycol ether moiety, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene moiety, C₆₋₄₀ cycloalkylene moiety, C₂₋₂₀ alkylene glycol ether moiety, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 2 to 100; and wherein x is an integer ranging from 1 to
 1000. 7. The method of claim 6, wherein each Y is an independently selected ethylene moiety, propylene moiety, cyclohexene dimethanol moiety, or caprylene lactone moiety.
 8. The method of claim 6, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
 9. The method of claim 6, wherein the compound has a weight ranging from 400 to 30000 Daltons.
 10. The method of claim 6, wherein the compound has a weight ranging from 500 to 30000 Daltons.
 11. A method comprising the step: adding a compound to: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent; to thereby improve the respective anti-wear properties, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁-22 alkyl moiety, C₆₋₄₀ cycloalkyl moiety, C₃₋₂₀ methoxy alkyl glycol ether moiety, C₃₋₂₀ alkyl glycol ether moiety, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene moiety, C₆₋₄₀ cycloalkylene moiety, C₂₋₂₀ alkylene glycol ether moiety, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 2 to 100; and wherein x is an integer ranging from 1 to
 1000. 12. The method of claim 11, wherein each Y is an independently selected ethylene moiety, propylene moiety, cyclohexene dimethanol moiety, or caprylene lactone moiety.
 13. The method of claim 11, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
 14. The method of claim 11, wherein the compound has a weight ranging from 400 to 30000 Daltons.
 15. The method of claim 11, wherein the compound has a weight ranging from 500 to 30000 Daltons.
 16. A method comprising the step: adding a compound to: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent; to thereby improve the respective anti-wear properties, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl moiety, C₆₋₄₀ cycloalkyl moiety, C₃₋₂₀ methoxy alkyl glycol ether moiety, C₃₋₂₀ alkyl glycol ether moiety, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene moiety, C₆₋₄₀ cycloalkylene moiety, C₂₋₂₀ alkylene glycol ether moiety, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer ranging from 2 to 100; wherein each Z is independently selected from the group consisting of S and O; and wherein x is an integer ranging from 1 to
 1000. 17. The method of claim 16, wherein each Y is an independently selected ethylene moiety, propylene moiety, cyclohexene dimethanol moiety, or caprylene lactone moiety.
 18. The method of claim 16, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
 19. The method of claim 16, wherein the compound has a weight ranging from 400 to 30000 Daltons.
 20. The method of claim 16, wherein the compound has a weight ranging from 500 to 30000 Daltons.
 21. A method comprising the step: adding a compound to: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent; to thereby improve the respective anti-wear properties, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₁₋₂₂ alkyl moiety, C₆₋₄₀ cycloalkyl moiety, C₃₋₂₀ methoxy alkyl glycol ether moiety, C₃₋₂₀ alkyl glycol ether moiety, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene moiety, C₆₋₄₀ cycloalkylene moiety, C₂₋₂₀ alkylene glycol ether moiety, or C₃₋₄₀ alkylene lactone moiety; wherein Y₁ and Y₂ are different; wherein each m is an independently selected integer ranging from 1 to 100; wherein m₁+m₂=3 or more; wherein each Z is independently selected from the group consisting of S, H, O, and nothing; and wherein each x is an independently selected integer ranging from 1 to
 1000. 22. The method of claim 21, wherein each Y is an independently selected ethylene moiety, propylene moiety, cyclohexene dimethanol moiety, or caprylene lactone moiety.
 23. The method of claim 21, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
 24. The method of claim 21, wherein the compound has a weight ranging from 400 to 30000 Daltons.
 25. The method of claim 21, wherein the compound has a weight ranging from 500 to 30000 Daltons.
 26. A method comprising the step: adding a compound to: gear oil, grease, engine oil, combustion-engine lubricant, automatic transmission fluid, two-cycle engine lubricant, marine-engine lubricant, or anti-wear agent; to thereby improve the respective anti-wear properties, the compound having the structure:

wherein each R is an independently selected alkylphenol-free moiety that is a C₆₋₄₀ cycloalkyl moiety, C₃₋₂₀ methoxy alkyl glycol ether moiety, C₃₋₂₀ alkyl glycol ether moiety, or Y—OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C₂₋₄₀ alkylene moiety, C₆₋₄₀ cycloalkylene moiety, C₂₋₂₀ alkylene glycol ether moiety, or C₃₋₄₀ alkylene lactone moiety; wherein each m is an independently selected integer that is 2 or more; and wherein x is an integer ranging from 1 to
 1000. 27. The method of claim 26, wherein each Y is an independently selected ethylene moiety, propylene moiety, cyclohexene dimethanol moiety, or caprylene lactone moiety.
 28. The method of claim 26, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
 29. The method of claim 26, wherein the compound has a weight ranging from 400 to 30000 Daltons.
 30. The method of claim 26, wherein the compound has a weight ranging from 500 to 30000 Daltons.
 31. The method of claim 21, wherein each Z is independently selected from the group consisting of S, H, and
 0. 32. The method of claim 1, wherein the compound is added in an amount ranging from 5% to 10% by weight.
 33. The method of claim 1, wherein the compound is added in an amount of about 2.6% by weight.
 34. The method of claim 1, wherein the compound is added in an amount ranging from 0.5% by weight to 2.6% by weight. 